Synlett 2023; 34(18): 2205-2209
cluster
Modern Boron Chemistry: 60 Years of the Matteson Reaction
Preparation and Use of (γ,γ-Dioxyallyl)boronates
Soshi Nishino
a
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Yuji Nishii
a
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
a
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
b
Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan
› Institutsangaben
Abstract
A copper-catalyzed stereoselective 1,4-acylboration of α,β-unsaturated esters with B2 pin2 and pivalic anhydride has been developed to afford the corresponding (E )-allylboronates with two distinct oxygenated functionalities at the γ positions, which are difficult to prepare by other means. The chemoselective post functionalizations of Bpin and pivalate moieties in the product are also demonstrated.
Key words allylboronate - borylation - conjugate addition - copper - stereoselectivity
References and Notes
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7 In the case with (i -PrCO)2 O, the Piv group derived from CsOPiv was also incorporated into the product, and the Piv-derived 1,4-acylboration product was also detected in ca. 5% 1 H NMR yield. We also tried the reaction with a 1:1 mixture of Piv2 O and Ac2 O. The corresponding Piv- and Ac-derived 1,4-acylboration products were formed in 21% and 2%, yields, respectively. Additionally, the protoboration byproduct 3a was also detected in 40% yield. Given that 3a mainly arose from the Ac-derived 1,4-acylboration product via in situ hydrolysis, the electrophilic trapping ability of Ac2 O is higher than that of Piv2 O.
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Experimental Procedures and Characterization Data
Synthesis of 2a (Scheme [4, 0 ].25 mmol scale)
Cu(OAc)2 (4.5 mg, 0.025 mmol), P(3,5-(CF3 )2 C6 H3 )3 (33.5 mg, 0.050 mmol), and KOPiv (105.2 mg, 0.75 mmol) were placed in a 20 mL Schlenk tube, which was filled with nitrogen by using the Schlenk technique. CPME (1.0 mL) was then added to the tube, and the suspension was stirred for 15 min at ambient temperature. Bis(pinacolato)diboron (158.7 mg, 0.63 mmol) was then added in one portion, and the resulting solution was stirred at the same temperature. After 5 min, pivalic anhydride (69.8 mg, 0.38 mmol) and methyl (E )-5-phenylpent-2-enoate (1a , 40.5 mg, 0.25 mmol) were added dropwise. The reaction solution was stirred at room temperature for additional 18 h. The resulting mixture was directly filtered through a short pad of neutral alumina and Na2 SO4 . The filtrate was evaporated in vacuo and purified by silica gel column chromatography on neutral silica gel with hexane/ethyl acetate (20/1 → 10/1, v/v) and GPC (CHCl3 ) to give 1-methoxy-5-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-1-en-1-yl pivalate (2a , 82.5 mg, 0.21 mmol) in 82% yield with >99:1 E /Z ratio.
(E )-1-Methoxy-5-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-1-en-1-yl pivalate ((E )-2a)
82.5 mg (82%); colorless oil. 1 H NMR (400 MHz, CDCl3 ): δ = 7.27–7.23 (m, 2 H), 7.21–7.19 (m, 2 H), 7.15 (t, J = 7.1 Hz, 1 H), 4.34 (d, J = 9.9 Hz, 1 H), 3.55 (s, 3 H), 2.74 (ddd, J = 13.6, 10.5, 5.4 Hz, 1 H), 2.59 (ddd, J = 13.6, 10.4, 6.0 Hz, 1 H), 2.09–2.03 (m, 1 H), 1.89–1.80 (m, 1 H), 1.73–1.65 (m, 1 H), 1.28 (s, 9 H), 1.25 (s, 12 H). 13 C{1 H} NMR (100 MHz, CDCl3 ): δ = 176.5, 150.6, 142.9, 128.7, 128.3, 125.6, 98.2, 83.3, 57.1, 39.1, 35.4, 33.4, 27.2, 24.9, 24.8, 20.5 (br). 11 B NMR (128 MHz, CDCl3 ,): δ = 32.7. HRMS (APCI): m/z [M + H]+ calcd for C23 H36 BO5 : 403.2654; found: 403.2666.
15 We preliminarily tested several reported conditions, including simple heating, Sc(OTf)3 catalyst, and ZnBr2 catalyst, for the allylation of benzaldehyde with 2a , 6 , and 7 . However, the allylic boronates just decomposed, and the corresponding homoallylic alcohols were not detected at all. Additional investigations are still necessary.
16 We preliminarily tried enantioselective conditions using several chiral phosphine ligands. However, the maximum enantiomeric ratio was 75:25 with a phosphoramidite ligand. See the Supporting Information for more details.
